EP0894841B1 - Adhesive tape - Google Patents
Adhesive tape Download PDFInfo
- Publication number
- EP0894841B1 EP0894841B1 EP98113152A EP98113152A EP0894841B1 EP 0894841 B1 EP0894841 B1 EP 0894841B1 EP 98113152 A EP98113152 A EP 98113152A EP 98113152 A EP98113152 A EP 98113152A EP 0894841 B1 EP0894841 B1 EP 0894841B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive tape
- pressure
- polyurethane
- weight
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002390 adhesive tape Substances 0.000 title claims description 41
- 239000004814 polyurethane Substances 0.000 claims description 35
- 229920002635 polyurethane Polymers 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 230000003712 anti-aging effect Effects 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 229920006122 polyamide resin Polymers 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 239000012763 reinforcing filler Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 235000011941 Tilia x europaea Nutrition 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 description 11
- 239000004571 lime Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 150000004072 triols Chemical class 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910000267 dualite Inorganic materials 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000011514 reflex Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2843—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including a primer layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
Definitions
- the invention describes a self-adhesive tape that is adhesive on both sides can perform gap-bridging sealing functions, on the other hand adhesive strength achieved, as they are typical for commercially available high-performance adhesive tapes.
- the product is suitable for achieving cold and heat-resistant bonds.
- DE-PS 2105877 shows an adhesive tape which consists of a carrier, on at least one side with a microcellular, pressure-sensitive adhesive is coated and the adhesive layer contains a nucleating agent, the cells the adhesive layer are closed and completely distributed in the adhesive layer.
- This tape can adhere to the irregular surface on which it is placed adapt and thus lead to a relatively permanent bond shows on the other hand even a relatively small recovery if it is half the original thickness has been squeezed.
- the voids in the adhesive offer Approaches for lateral entry of solvents and water into the glue joint, what For example, in the case of glued-on strips in automobile construction, this is very undesirable. Farther the complete passage of solvents or water through the whole Adhesive tape cannot be excluded.
- EP 601 582 A describes an adhesive tape which consists of a foamed There is an elastomer core to which a pressure-sensitive adhesive layer is applied has been.
- the tape core can absorb moisture or solvents like a sponge. This can weaken the bond strength.
- the foamed elastomer core in the bonds restores forces, which can lead to premature failure of the bonds.
- the adhesive tapes mentioned have in common that the absorbable shear forces act on the glued connection, for many applications are not sufficient to a permanent connection between the surface and the adhesive tape to ensure mounting object. This is especially the case at lower temperatures the use of such tapes is very limited because embrittlement occurs at low temperatures, so that the adhesive tape does not is more able to maintain the desired bond.
- Adhesive tapes mentioned are not able to gap widths of more than 0.5 cm to bridge and seal. Adhesive tapes that are able to do this, e.g. Butyl tapes, achieve very low strengths against shear and tilt shear stresses, especially at elevated temperatures.
- a laminate of a polyurethane and a pressure-sensitive is also known Adhesive layer.
- Adhesive layer Such a laminate is described, for example, in WO 86/00536, one Description for a tablet packaging or dosage form disclosed. there becomes a discontinued polyester film with a self-adhesive coating provided, which encloses a tablet and at the same time with the tablet on the skin of the user is glued.
- a double-sided adhesive tape based on a polyurethane backing as described above and a pressure-sensitive laminated on both sides Adhesive layer is not described in the cited documents, but it would have been also the disadvantage of elastic restoring forces of the wearer, which are not absorbed can and would therefore lead to a weakening of the bond strength.
- the invention has for its object to provide a self-adhesive tape that the Not disadvantages of the prior art, or at least not to the extent and yet not in terms of usability similar to the aforementioned products is restricted.
- the invention proposes a pressure-sensitive, bilateral Self-adhesive tape coated with adhesive, the backing of which is formulated by a cross-linked, non-foamed polyurethane is formed.
- Formulation constituents of the carrier are a crosslinked, non-foamed polyurethane, fillers and optionally other auxiliaries.
- the proportion of polyurethane in the carrier is up to 50% by weight, preferably 30% by weight to 40% by weight, the polyurethane being free from plasticizers.
- the fillers make up 50% to 70% by weight of the carrier.
- the selection of the isocyanate component of the polyurethane is based on the properties of the carrier to be specifically set. For example, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, mixtures of the isocyanates mentioned or chemically derived isocyanates, for example dimerized or trimerized types.
- the selection of the component reacting with the isocyanate also depends on the properties of the support to be set depending on the desired requirement profile.
- the hydroxyl-functionalized polybutadienes, the polyester diols, the polyester triols, the polyester polyols, the polyether diols, the polyether triols, the polyether polyols, the polyether diamines, the polyether triamines or the polyether polyamines have a molecular weight M g 1000 1000 g / mol.
- components can also use other starting materials to form the polyurethane without leaving the inventive concept.
- Polyurethanes as described above are state of the art in manufacturing and, for example in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21: Polyurethanes" described.
- an NCO / OH ratio of 1.0 to 1.3, preferably 1.0 to 1.1.
- the preferred mono-ol-OH portion of the total OH portion i.e. the preferred chain termination portion lies between 5% and 40%, in particular between 10% and 30%.
- Both fillers such as carbon black, as well as non-reinforcing, such as chalk or barium sulfate.
- Further examples are talc, mica, pyrogenic silica, silicates, zinc oxide, micro glass balls, Hollow micro glass balls and / or micro plastic balls of all kinds. Also mixtures of the substances mentioned can be used.
- anti-aging agents which, depending on the application, can come from the class of discoloring or non-discoloring anti-aging agents, in the range between 0% by weight and 5% by weight, and known light stabilizers in the range between 0% by weight and 5% by weight or ozone protection agents in the range between 0% by weight and 5% by weight are mixed.
- drying agents such as calcium oxide or molecular sieve zeolites, can also be added to the formulation, in particular in the range between 0% by weight and 10% by weight.
- all of the auxiliaries mentioned can either alone or in any combination with one another to produce the polyurethane composition be used in order to obtain an optimal adjustment to the use.
- the blackening is also particularly great is required by the motor vehicle industry, easily possible.
- the carrier mixture is preferably prepared in a planetary mixer or dissolver. In order to achieve freedom from bubbles, vacuum is used. The viscosity of the mixture is adjusted so that it is in the range between 10 -1 and 10 3 Pa * s at room temperature. Solvent-free processing is preferably carried out.
- the mixture can then in a conventional coating machines any thickness between 0.1 mm to 50 mm, preferably between 0.4 mm and 20 mm.
- the chemical crosslinking then takes place in the drying tunnel, preferably at Temperatures from room temperature to 120 ° C, depending on the selected polyurethane formulation and the amount of catalyst.
- the application weight of the adhesive composition can likewise be selected as desired within the range from 10 g / m 2 to 250 g / m 2 , preferably 40 g / m 2 to 150 g / m 2 .
- adhesion promoters or additional layers of lacquer can be used to increase the anchoring of the adhesive on the carrier.
- the paint preferably comes from the group of polyamide, epoxy, phenol, urea-formaldehyde, melamine-formaldehyde or polyurethane resins.
- a corona pretreatment can also be carried out.
- a combination of the methods listed is also possible in order to achieve particularly firm anchorages.
- the adhesive can be applied directly, in an indirect transfer process or by coextrusion the carrier can be applied from solution, dispersion or melt.
- a the "inverse" application method is particularly preferred.
- the process is the dried and coated on release paper or release film crosslinked adhesive and submitted with the not yet hardened, pasty or liquid Polyurethane mass with the help of two-component mixing technology in the desired layer thickness coated. Even before the hardening or networking of the Polyurethane mass becomes a second adhesive mass, which is also already spread out, dried and cross-linked on release paper or release film located against the spread Laminated polyurethane mass.
- the curing or crosslinking then takes place the polyurethane mass in the dry run through at a temperature between Room temperature and 120 ° C, depending on the selected polyurethane formulation and the Amount of catalyst.
- a self-adhesive tape as described above consisting essentially of a laminate of a polyurethane composition formulated according to the invention and a pressure-sensitive adhesive layer and characterized by a three-layer structure Adhesive layer / formulated polyurethane mass / adhesive layer, is in the prior art not prescribed.
- the formulation with fillers leads to the excellent product properties described above.
- the fillers take part of the elastic backing from the polyurethane backing Restoring forces and thus contribute to the permanent bond strength of the bonds at.
- the self-adhesive tape shows excellent properties, even for the specialist were unpredictable. Due to the high flexibility of the wearer fits the adhesive tape will adhere very well to uneven surfaces if it has a certain Pressure on this is pressed. This creates a very permanent connection between the adhesive tape and the surface, even at high shear forces act on the self-adhesive tape, not fail. Because of the missing side open The possible penetration of solvents or water also becomes voids in the carrier prevented in the tape with all its known disadvantages. Because the tape can be manufactured according to the invention in thicknesses of 2 cm and more, it is also available as self-adhesive, gap-bridging sealing tape can be used.
- the good heat and aging stability of the adhesive tape caused by the non-foamed carrier consistency that allows moisture and atmospheric oxygen to penetrate prevented, also allows use at higher temperatures from 70 ° C to 100 ° C.
- Cold and heat loads are, for example, when gluing decorative strips or mirroring in the automotive industry because the vehicles are sometimes also in very cold zones or very warm regions of the earth with high solar radiation be driven.
- the invention is used not only in the automotive industry but also in Furniture and construction industry, where mirrors, strips or panels are also permanently with the Are to be anchored to the ground.
- Table 1 lists the materials used to manufacture the carrier, each with its trade name and manufacturer. The chemicals mentioned are all freely available commercially. The raw materials are used in different mixing ratios depending on the application of the self-adhesive tape.
- Materials used to manufacture the carrier with trade names and manufacturers trade name Chemical basis Manufacturer / supplier
- Arcol 1010 Polyether diol ARCO Arcol 1042 ® Polyether triol ARCO Baycoll BT 5035 ® Polyether triol Bavarian Poly bd R45HT ® Hydroxyl terminated polybutadiene Eleven Atochem Lutensol AO7 ® ethoxylated C 13 C 15 oxo alcohol BASF 1-Dodecanol ® 1-dodecanol Aldrich Omyacarb 4 BG ® chalk OMYA Barite flour N ® barium sulfate Alberti Talc Prever ® talc Luzenac Zinc oxide resin seal GR ® zinc oxide Heubach Dualite M 6001 AE ® coated plastic balls OM
- Baycoll BT 5035 40.0 kg Lutensol AO7 3.2 kg Omyacarb 4BG 47.0 kg fine white lime 3.0 kg Aerosil R202 2.0 kg Desmodur CD 4.7 kg DBTL 0.1 kg
- Baycoll BT 5035 40.0 kg 1-dodecanol 1.2 kg Omyacarb 4BG 49.0 kg fine white lime 3.0 kg Aerosil R202 2.0 kg Desmodur CD 4.7 kg DBTL 0.1 kg
- Arcol 1042 42.0 kg Lutensol AO7 1.5 kg Omyacarb 4BG 48.8 kg fine white lime 3.0 kg Printex 30 1.0 kg Vestanat IPDI 3.4 kg DBTL 0.3 kg
- Arcol 1042 42.0 kg Omyacarb 4BG 51.3 kg fine white lime 3.0 kg Printex 30 1.0 kg Vestanat IPDI 2.4 kg DBTL 0.3 kg
- the pastes are spread onto a commercially available coating system on commercially available paper that has been siliconized on both sides to form a web of 1 mm thickness and then pass through a drying channel at a temperature of from room temperature to 120 ° C. and a residence time of 10 minutes to 30 minutes to form an elastomer networked.
- the carriers After curing and subsequent storage for one week at room temperature, the carriers have a Shore A hardness of 10 to 60, a glass transition temperature in the range from -60 ° C to -30 ° C and a tensile strength of greater than 1 N / mm 2 with an elongation at break of less than 500%.
- the material is then coated on both sides with 50 g / m 2 of the Durotac 280-1753 polyacrylate composition from National Starch on both sides.
- the coating with the solvent mass takes place after an in-line corona treatment directly on the carrier. It is dried and crosslinked at 100 ° C.
- the double-sided adhesive tape thus obtained is covered on one side with release paper.
- the polyacrylate composition is first opened Release paper or release film spread and dried and crosslinked at 100 ° C.
- the Coating with the polyurethane mixture takes place directly on the spread polyacrylate mass.
- the polyurethane composition cures or crosslinks second polyacrylate mass, which has also already been spread out, dried and crosslinked on release paper or release film, laminated against the polyurethane mass.
- the polyurethane mass is then cured or crosslinked in a dry channel run at a temperature between room temperature and 120 ° C of the selected polyurethane formulation and the amount of catalyst.
- the double-sided adhesive tape is characterized by high adhesive strength with simultaneous high shear strength and the bonds created with it have excellent Low-temperature impact strength.
- the material seals well against moisture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Die Erfindung beschreibt ein beidseitig klebendes Selbstklebeband, das einerseits spaltüberbrückende Dichtungsfunktionen wahrnehmen kann, andererseits Klebfestigkeiten erreicht, wie sie für im Handel befindliche Hochleistungsklebebänder typisch sind. Das Produkt ist sowohl zur Erzielung kälte- als auch wärmefester Verklebungen geeignet.The invention describes a self-adhesive tape that is adhesive on both sides can perform gap-bridging sealing functions, on the other hand adhesive strength achieved, as they are typical for commercially available high-performance adhesive tapes. The product is suitable for achieving cold and heat-resistant bonds.
Um hohe Festigkeiten gegenüber Abschälen und Scherkräften zu erreichen, ist der Einsatz unterschiedlicher Klebebänder bekannt.In order to achieve high strengths against peeling and shear forces, the use is different tapes known.
In der DE-PS 2105877 wird ein Klebeband aufgezeigt, das aus einem Träger besteht, der auf mindestens einer Seite mit einem mikrozellulären, druckempfindlichen Klebstoff beschichtet ist und dessen Klebstoffschicht einen Keimbildner enthält, wobei die Zellen der Klebstoffschicht geschlossen und vollständig in der Klebstoffschicht verteilt sind. Dieses Klebeband kann sich der unregelmäßigen Oberfläche, auf die es gebracht wird, anpassen und somit zu einer relativ dauerhaften Verklebung führen, zeigt andererseits auch nur eine relativ geringe Erholung, wenn es auf die Hälfte der ursprünglichen Dicke zusammengedrückt worden ist. Die Hohlräume in der Klebmasse bieten allerdings Ansätze für seitliches Eintreten von Lösungsmitteln und Wasser in die Klebefuge, was beispielsweise bei aufgeklebten Leisten im Automobilbau sehr unerwünscht ist. Weiterhin kann der vollständige Durchtritt von Lösungsmitteln oder Wasser durch das gesamte Klebeband nicht ausgeschlossen werden.DE-PS 2105877 shows an adhesive tape which consists of a carrier, on at least one side with a microcellular, pressure-sensitive adhesive is coated and the adhesive layer contains a nucleating agent, the cells the adhesive layer are closed and completely distributed in the adhesive layer. This tape can adhere to the irregular surface on which it is placed adapt and thus lead to a relatively permanent bond shows on the other hand even a relatively small recovery if it is half the original thickness has been squeezed. However, the voids in the adhesive offer Approaches for lateral entry of solvents and water into the glue joint, what For example, in the case of glued-on strips in automobile construction, this is very undesirable. Farther the complete passage of solvents or water through the whole Adhesive tape cannot be excluded.
In der EP 601 582 A wird ein Klebeband beschrieben, das aus einem geschäumten Elastomerkern besteht, auf den eine druckempfindliche Klebstoffschicht aufgebracht wurde. EP 601 582 A describes an adhesive tape which consists of a foamed There is an elastomer core to which a pressure-sensitive adhesive layer is applied has been.
Auch hier sind die durch das Prinzip der Hohlräume bedingten Nachteile gegeben, daß der Klebebandkem wie ein Schwamm Feuchtigkeit oder Lösungsmittel aufsaugen kann. Dies kann zu einer Schwächung der Verbundfestigkeit führen. Weiterhin treten durch das Prinzip des geschäumten Elastomerkerns in den Verklebungen Rückstellkräfte auf, die zu einem vorzeitigen Versagen der Verklebungen führen können.Here too, the disadvantages caused by the principle of cavities are that the tape core can absorb moisture or solvents like a sponge. This can weaken the bond strength. Continue to step through the principle of the foamed elastomer core in the bonds restores forces, which can lead to premature failure of the bonds.
Den genannten Klebebändern ist gemeinsam, daß die aufnehmbaren Scherkräfte, die auf die geklebte Verbindung einwirken, für viele Einsatzfälle nicht ausreichend sind, um eine dauerhafte Verbindung zwischen Untergrund und dem mittels des Klebebandes zu montierenden Gegenstand zu gewährleisten. So ist insbesondere bei tieferen Temperaturen die Verwendung derartiger Klebebänder nur sehr eingeschränkt möglich, weil bei tiefen Temperaturen eine Versprödung des Trägers auftritt, so daß das Klebeband nicht mehr in der Lage ist, die gewünschte Verklebung aufrechtzuerhalten.The adhesive tapes mentioned have in common that the absorbable shear forces act on the glued connection, for many applications are not sufficient to a permanent connection between the surface and the adhesive tape to ensure mounting object. This is especially the case at lower temperatures the use of such tapes is very limited because embrittlement occurs at low temperatures, so that the adhesive tape does not is more able to maintain the desired bond.
Außerdem sind die genannten Klebebänder nicht in der Lage, Spaltbreiten von mehr als 0,5 cm zu überbrücken und abzudichten. Klebebänder, die dazu in der Lage sind, z.B. Butylbänder, erreichen nur sehr geringe Festigkeiten gegenüber Scher- und Kippscherbeanspruchungen, insbesondere bei erhöhten Temperaturen.In addition, the adhesive tapes mentioned are not able to gap widths of more than 0.5 cm to bridge and seal. Adhesive tapes that are able to do this, e.g. Butyl tapes, achieve very low strengths against shear and tilt shear stresses, especially at elevated temperatures.
Bekannt ist weiterhin ein Laminat aus einem Polyurethan und einer druckempfindlichen Klebeschicht. Ein solches Laminat wird beispielsweise in der WO 86/00536, einer Beschreibung für eine Tablettenverpackung bzw. -darreichungsform, offenbart. Dabei wird eine nicht weiter aufbereitete Polyesterfolie mit einer selbstklebenden Beschichtung versehen, die eine Tablette umschließt und gleichzeitig mit der Tablette auf der Haut des Anwenders verklebt wird.A laminate of a polyurethane and a pressure-sensitive is also known Adhesive layer. Such a laminate is described, for example, in WO 86/00536, one Description for a tablet packaging or dosage form disclosed. there becomes a discontinued polyester film with a self-adhesive coating provided, which encloses a tablet and at the same time with the tablet on the skin of the user is glued.
Aus US 5,127,974 ist eine Folie zum vorübergehenden Schutz der lackierten Oberflächen von Automobilen bekannt, die u.a. auch die Verwendung von Polyurethan zur Herstellung der Trägerfolie vorschlägt. Auf die Trägerfolie ist dann eine druckempfindliche Klebmasse aufgebracht. Dies Laminat aus Folie und Klebmasse wird nach der Entfernung einer die Klebmasse schützenden Schicht auf der lackierten Oberfläche aufgebracht. From US 5,127,974 is a film for the temporary protection of the painted surfaces known from automobiles that also the use of polyurethane for Production of the carrier film suggests. A pressure-sensitive is then on the carrier film Adhesive applied. This laminate of film and adhesive is made after Removal of a layer protecting the adhesive from the painted surface applied.
Ein beidseitig klebendes Selbstklebeband, basierend auf einem Polyurethanträger gemäß obiger Beschreibung und einer beidseitig auflaminierten druckempfindlichen Klebeschicht, wird in den genannten Schriften nicht beschrieben, hätte aber darüber hinaus den Nachteil elastischer Rückstellkräfte des Trägers, die nicht aufgefangen werden können und daher zu einer Schwächung der Verbundfestigkeit führen würden.A double-sided adhesive tape based on a polyurethane backing as described above and a pressure-sensitive laminated on both sides Adhesive layer, is not described in the cited documents, but it would have been also the disadvantage of elastic restoring forces of the wearer, which are not absorbed can and would therefore lead to a weakening of the bond strength.
Der Erfindung liegt die Aufgabe zugrunde, ein Selbstklebeband zu schaffen, das die Nachteile des Standes der Technik nicht, oder zumindest nicht in dem Umfang aufweist und das dennoch nicht in seiner Einsatzfähigkeit ähnlich den vorgenannten Produkten eingeschränkt ist.The invention has for its object to provide a self-adhesive tape that the Not disadvantages of the prior art, or at least not to the extent and yet not in terms of usability similar to the aforementioned products is restricted.
Zur Lösung dieser Aufgabe schlägt die Erfindung ein druckempfindliches, beidseitig mit Klebemassen beschichtetes Selbstklebeband vor, dessen Träger von einem formulierten, vernetzten, nicht geschäumten Polyurethan gebildet ist.To achieve this object, the invention proposes a pressure-sensitive, bilateral Self-adhesive tape coated with adhesive, the backing of which is formulated by a cross-linked, non-foamed polyurethane is formed.
Rezeptierungsbestandteile des Trägers sind ein vernetztes, nicht geschäumtes Polyurethan,
Füllstoffe und gegebenenfalls weitere Hilfsstoffe.
Der Anteil des Polyurethans am Träger beträgt bis zu 50 Gew.-%, vorzugsweise 30
Gew.-% bis 40 Gew.-%, wobei das Polyurethan weichmacherfrei ist.
Die Füllstoffe machen 50 Gew.-% bis 70 Gew.-% des Trägers aus.Formulation constituents of the carrier are a crosslinked, non-foamed polyurethane, fillers and optionally other auxiliaries.
The proportion of polyurethane in the carrier is up to 50% by weight, preferably 30% by weight to 40% by weight, the polyurethane being free from plasticizers. The fillers make up 50% to 70% by weight of the carrier.
Die Auswahl der Isocyanat-Komponente des Polyurethans richtet sich nach den gezielt
einzustellenden Eigenschaften des Trägers. In Frage kommen z.B. Toluylendiisocyanat,
Diphenylmethan-4,4'-diisocyanat, Dicyclohexylmethan-4,4'-diisocyanat, Hexamethylendiisocyanat,
Isophorondiisocyanat, Gemische der genannten Isocyanate oder chemisch
daraus abgeleitete Isocyanate, z.B. dimerisierte oder trimerisierte Typen.
Die Auswahl der mit dem Isocyanat reagierenden Komponente richtet sich ebenfalls
nach den in Abhängigkeit vom gewünschten Anforderungsprofil einzustellenden Eigenschaften
des Trägers. Beispielsweise kommen in Frage alle Polyesterdiole, -triole
und - polyole, Polyetherdiole, -triole und -polyole, Polyetherdiamine, -triamine, -polyamine,
hydroxyl-funktionalisiertes Polybutadien sowie alle einwertigen Alkohole (Mono-ole),
einwertigen Amine (Mono-amine), Polyether-mono-ole, Polyether-mono-amine oder aus
den vier letztgenannten Gruppen abgeleitete Produkte. The selection of the isocyanate component of the polyurethane is based on the properties of the carrier to be specifically set. For example, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, mixtures of the isocyanates mentioned or chemically derived isocyanates, for example dimerized or trimerized types.
The selection of the component reacting with the isocyanate also depends on the properties of the support to be set depending on the desired requirement profile. For example, all polyester diols, triols and polyols, polyether diols, triols and polyols, polyether diamines, triamines, polyamines, hydroxyl-functionalized polybutadiene and all monohydric alcohols (monools), monohydric amines (monoamines) , Polyether-mono-ole, Polyether-mono-amine or products derived from the last four groups.
Als vorteilhaft hat sich gezeigt, wenn die hydroxyl-funktionalisierten Polybutadiene, die Polyesterdiole, die Polyestertriole, die Polyesterpolyole, die Polyetherdiole, die Polyethertriole, die Polyetherpolyole, die Polyetherdiamine, die Polyethertriamine oder die Polyetherpolyamine ein Molekulargewicht Mg ≥ 1000 g/mol aufweisen.It has proven to be advantageous if the hydroxyl-functionalized polybutadienes, the polyester diols, the polyester triols, the polyester polyols, the polyether diols, the polyether triols, the polyether polyols, the polyether diamines, the polyether triamines or the polyether polyamines have a molecular weight M g 1000 1000 g / mol.
Neben den oben aufgezählten Isocyanat-Komponenten und den damit reagierenden Komponenten können aber auch andere Edukte zur Bildung des Polyurethans verwendet werden, ohne den Erfindungsgedanken zu verlassen.In addition to the isocyanate components listed above and the reacting with them However, components can also use other starting materials to form the polyurethane without leaving the inventive concept.
Um die Reaktion zwischen der Isocyanat-Komponente und der mit dem Isocyanat reagierenden Komponente zu beschleunigen, können alle dem Fachmann bekannten Katalysatoren, wie z.B. tertiäre Amine oder zinnorganische Verbindungen eingesetzt werden.To the reaction between the isocyanate component and that reacting with the isocyanate To accelerate the component, all catalysts known to the person skilled in the art, such as. tertiary amines or organotin compounds are used.
Polyurethane wie oben beschrieben sind in der Herstellung Stand der Technik und beispielsweise in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21: Polyurethanes" beschrieben.Polyurethanes as described above are state of the art in manufacturing and, for example in "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21: Polyurethanes" described.
Die Formulierung von Polyurethan-Massen ist ebenfalls Stand der Technik und wird besonders bei der Herstellung von Dichtmassen angewendet (vgl. "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23: Sealing Materials").The formulation of polyurethane compositions is also state of the art and will especially used in the production of sealing compounds (cf. "Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 23: Sealing Materials ").
In einer besonders bevorzugten Ausführungsform des Selbstklebebands wird zur Bildung des Polyurethans ein NCO/OH-Verhältnis von 1,0 bis 1,3 eingestellt, vorzugsweise 1,0 bis 1,1.In a particularly preferred embodiment of the self-adhesive tape is used for formation of the polyurethane, an NCO / OH ratio of 1.0 to 1.3, preferably 1.0 to 1.1.
Der bevorzugte Mono-ol-OH-Anteil am Gesamt-OH-Anteil, d.h., der bevorzugte Kettenabbruchsanteil, liegt zwischen 5 % und 40 %, insbesondere zwischen 10 % und 30 %.The preferred mono-ol-OH portion of the total OH portion, i.e. the preferred chain termination portion lies between 5% and 40%, in particular between 10% and 30%.
Als Füllstoffe können sowohl verstärkende, wie zum Beispiel Ruß, als auch nicht verstärkende, wie zum Beispiel Kreide oder Bariumsulfat, eingesetzt werden. Weitere Beispiele sind Talkum, Glimmer, pyrogene Kieselsäure, Silikate, Zinkoxid, Mikrovollglaskugeln, Mikrohohlglaskugeln und/oder Mikrokunststoffkugeln aller Art. Auch Mischungen der genannten Stoffe können eingesetzt werden. Both fillers, such as carbon black, as well as non-reinforcing, such as chalk or barium sulfate. Further examples are talc, mica, pyrogenic silica, silicates, zinc oxide, micro glass balls, Hollow micro glass balls and / or micro plastic balls of all kinds. Also mixtures of the substances mentioned can be used.
Zur Erhöhung der Alterungsstabilität des Klebebandes kann dies mit üblichen Alterungsschutzmitteln,
die je nach Anwendungsfall aus der Klasse der verfärbenden oder
der nicht verfärbenden Alterungsschutzmittel stammen können, und zwar im Bereich
zwischen 0 Gew.-% und 5 Gew.-% sowie bekannten Lichtschutzmitteln im Bereich zwischen
0 Gew.-% und 5 Gew.-% oder Ozonschutzmitteln im Bereich zwischen 0 Gew.-%
und 5 Gew.-% abgemischt werden.
Zur Erzielung von Blasenfreiheit können darüber hinaus Trockenmittel, wie beispielsweise
Calciumoxid oder Molekularsieb-Zeolithe der Rezeptur beigemischt werden, insbesondere
im Bereich zwischen 0 Gew.-% und 10 Gew.-%.To increase the aging stability of the adhesive tape, this can be done with conventional anti-aging agents, which, depending on the application, can come from the class of discoloring or non-discoloring anti-aging agents, in the range between 0% by weight and 5% by weight, and known light stabilizers in the range between 0% by weight and 5% by weight or ozone protection agents in the range between 0% by weight and 5% by weight are mixed.
To achieve freedom from bubbles, drying agents, such as calcium oxide or molecular sieve zeolites, can also be added to the formulation, in particular in the range between 0% by weight and 10% by weight.
Alle genannten Hilfsstoffe können je nach Einsatzzweck des Selbstklebebandes entweder allein oder in beliebiger Kombination miteinander zur Herstellung der Polyurethanmasse eingesetzt werden, um eine optimale Abstimmung auf die Verwendung zu erhalten. Durch den Einsatz dieser Zusatzstoffe ist auch die Schwarzfärbung, wie sie insbesondere von der Kraftfahrzeugindustrie gefordert wird, problemlos möglich.Depending on the intended use of the self-adhesive tape, all of the auxiliaries mentioned can either alone or in any combination with one another to produce the polyurethane composition be used in order to obtain an optimal adjustment to the use. Through the use of these additives, the blackening is also particularly great is required by the motor vehicle industry, easily possible.
Die Anfertigung der Trägermischung findet vorzugsweise in einem Planetenmischer oder Dissolver statt. Um Blasenfreiheit zu erreichen, wird im Vakuumbetrieb gearbeitet. Die Viskosität der Mischung wird so eingestellt, daß sie bei Raumtemperatur im Bereich zwischen 10-1 und 103 Pa*s liegt. Vorzugsweise erfolgt eine lösungsmittelfreie Verarbeitung.The carrier mixture is preferably prepared in a planetary mixer or dissolver. In order to achieve freedom from bubbles, vacuum is used. The viscosity of the mixture is adjusted so that it is in the range between 10 -1 and 10 3 Pa * s at room temperature. Solvent-free processing is preferably carried out.
Die Mischung kann anschließend auf handelsüblichen Beschichtungsmaschinen in einer beliebigen Dicke zwischen 0,1 mm bis 50 mm ausgestrichen werden, vorzugsweise zwischen 0,4 mm und 20 mm.The mixture can then in a conventional coating machines any thickness between 0.1 mm to 50 mm, preferably between 0.4 mm and 20 mm.
Im Anschluß erfolgt die chemische Vernetzung im Trockenkanal, vorzugsweise bei Temperaturen von Raumtemperatur bis 120 °C, abhängig von der gewählten Polyurethanrezeptur und der Katalysatormenge.The chemical crosslinking then takes place in the drying tunnel, preferably at Temperatures from room temperature to 120 ° C, depending on the selected polyurethane formulation and the amount of catalyst.
Das Auftragsgewicht der Klebmasse ist ebenfalls je nach Einsatzzweck beliebig innerhalb des Bereiches von 10 g/m2 bis 250 g/m2, vorzugsweise 40 g/m2 bis 150 g/m2, wählbar. Depending on the intended use, the application weight of the adhesive composition can likewise be selected as desired within the range from 10 g / m 2 to 250 g / m 2 , preferably 40 g / m 2 to 150 g / m 2 .
Als Klebmassen können allgemein vorbekannte Klebmassen auf Kautschuk- oder Acrylatbasis verwendet werden.Generally known adhesives based on rubber or acrylate can be used as adhesives be used.
Um die Verankerung der Klebmasse auf dem Träger zu erhöhen, können bekannte
Haftvermittler oder zusätzliche Lackschichten eingesetzt werden. Der Lack stammt dabei
vorzugsweise aus der Gruppe der Polyamid-, Epoxid-, Phenol-, Harnstoff-Formaldehyd-,
Melamin-Formaldehyd- oder Polyurethanharze.
Alternativ dazu kann auch eine Corona-Vorbehandlung vorgenommen werden. Um
besonders feste Verankerungen zu erzielen, ist auch eine Kombination der aufgeführten
Verfahren möglich.Known adhesion promoters or additional layers of lacquer can be used to increase the anchoring of the adhesive on the carrier. The paint preferably comes from the group of polyamide, epoxy, phenol, urea-formaldehyde, melamine-formaldehyde or polyurethane resins.
Alternatively, a corona pretreatment can also be carried out. A combination of the methods listed is also possible in order to achieve particularly firm anchorages.
Die Klebmasse kann direkt, im indirekten Transferverfahren oder durch Coextrusion mit dem Träger aus der Lösung, Dispersion oder Schmelze aufgetragen werden. Eine besonders bevorzugte Auftragsform ist das "inverse" Auftragsverfahren. Bei diesem Verfahren wird die auf Trennpapier oder Trennfolie ausgestrichene, getrocknete und vernetzte Klebmasse vorgelegt und mit der noch nicht gehärteten, pastösen oder flüssigen Polyurethanmasse unter Zuhilfenahme der Zweikomponentenmischtechnik in der gewünschten Schichtdicke beschichtet. Noch vor der Härtung bzw. Vernetzung der Polyurethanmasse wird eine zweite Klebmasse, die sich ebenfalls bereits ausgestrichen, getrocknet und vernetzt auf Trennpapier oder Trennfolie befindet gegen die ausgestrichene Polyurethanmasse kaschiert. Anschließend erfolgt die Härtung bzw. Vernetzung der Polyurethanmasse im Trockenkanaldurchlauf bei einer Temperatur zwischen Raumtemperatur und 120 °C, abhängig von der gewählten Polyurethanrezeptur und der Katalysatormenge.The adhesive can be applied directly, in an indirect transfer process or by coextrusion the carrier can be applied from solution, dispersion or melt. A the "inverse" application method is particularly preferred. With this The process is the dried and coated on release paper or release film crosslinked adhesive and submitted with the not yet hardened, pasty or liquid Polyurethane mass with the help of two-component mixing technology in the desired layer thickness coated. Even before the hardening or networking of the Polyurethane mass becomes a second adhesive mass, which is also already spread out, dried and cross-linked on release paper or release film located against the spread Laminated polyurethane mass. The curing or crosslinking then takes place the polyurethane mass in the dry run through at a temperature between Room temperature and 120 ° C, depending on the selected polyurethane formulation and the Amount of catalyst.
Ein Selbstklebeband gemäß obiger Beschreibung, im wesentlichen bestehend aus einem Laminat aus einer erfindungsgemäß formulierten Polyurethan-Masse und einer druckempfindlichen Klebschicht sowie gekennzeichnet durch einen dreischichtigen Aufbau Klebschicht/formulierte Polyurethanmasse/Klebschicht, ist im Stand der Technik nicht vorbeschrieben.A self-adhesive tape as described above, consisting essentially of a laminate of a polyurethane composition formulated according to the invention and a pressure-sensitive adhesive layer and characterized by a three-layer structure Adhesive layer / formulated polyurethane mass / adhesive layer, is in the prior art not prescribed.
Die Formulierung mit Füllstoffen führt zu den oben beschriebenen hervorragenden Produkteigenschaften. Die Füllstoffe nehmen dem Polyurethanträger einen Teil seiner elastischen Rückstellkräfte und tragen damit zur dauerhaften Verbundfestigkeit der Verklebungen bei. The formulation with fillers leads to the excellent product properties described above. The fillers take part of the elastic backing from the polyurethane backing Restoring forces and thus contribute to the permanent bond strength of the bonds at.
Das Selbstklebeband zeigt hervorragende Eigenschaften, die auch für den Fachmann derartig nicht vorherzusehen waren. Aufgrund der hohen Flexibilität des Trägers paßt sich das Klebeband sehr gut unebenem Untergrund an, wenn es mit einem gewissen Druck auf diesen gepreßt wird. Auf diese Weise entsteht eine sehr dauerhafte Verbindung zwischen Klebeband und Untergrund, die auch bei hohen Scherkräften, die auf das Selbstklebeband einwirken, nicht versagt. Wegen der fehlenden seitlich offenen Hohlräume im Träger wird auch das mögliche Eindringen von Lösungsmitteln oder Wasser in das Klebeband mit all seinen bekannten Nachteilen verhindert. Da das Klebeband gemäß Erfindung in Dicken von 2 cm und mehr hergestellt werden kann, ist es auch als selbstklebendes, spaltüberbrückendes Abdichtband einsetzbar.The self-adhesive tape shows excellent properties, even for the specialist were unpredictable. Due to the high flexibility of the wearer fits the adhesive tape will adhere very well to uneven surfaces if it has a certain Pressure on this is pressed. This creates a very permanent connection between the adhesive tape and the surface, even at high shear forces act on the self-adhesive tape, not fail. Because of the missing side open The possible penetration of solvents or water also becomes voids in the carrier prevented in the tape with all its known disadvantages. Because the tape can be manufactured according to the invention in thicknesses of 2 cm and more, it is also available as self-adhesive, gap-bridging sealing tape can be used.
Aufgrund des sehr niedrigen Glaspunktes des Klebebandes sind Tieftemperatureinsätze bis - 40 °C möglich, weil die sonst zu beobachtende Versprödung bekannter Klebebänder nicht auftritt, so daß auch bei diesen extremen Temperaturen eine optimale Haftung des Klebebandes gewährleistet ist.Due to the very low glass point of the adhesive tape, it is used at low temperatures down to - 40 ° C because the otherwise observed embrittlement of known adhesive tapes does not occur, so that optimum adhesion even at these extreme temperatures the adhesive tape is guaranteed.
Die gute Wärme- und Alterungsstabilität des Klebebandes, hervorgerufen durch die nicht-geschäumte Trägerkonsistenz, die ein Eindringen von Feuchtigkeit und Luftsauerstoff verhindert, ermöglicht auch den Einsatz bei höheren Temperaturen von 70 °C bis 100 °C.The good heat and aging stability of the adhesive tape, caused by the non-foamed carrier consistency that allows moisture and atmospheric oxygen to penetrate prevented, also allows use at higher temperatures from 70 ° C to 100 ° C.
Kälte- und Wärmebelastbarkeiten werden beispielsweise bei der Verklebung von Zierleisten oder Spiegeln im Automobilbau gefordert, weil die Fahrzeuge teilweise auch in sehr kalten Zonen beziehungsweise sehr warmen Regionen der Erde mit hoher Sonneneinstrahlung gefahren werden.Cold and heat loads are, for example, when gluing decorative strips or mirroring in the automotive industry because the vehicles are sometimes also in very cold zones or very warm regions of the earth with high solar radiation be driven.
Die Verwendung der Erfindung erfolgt außer in der Automobilindustrie auch in der Möbel- und Bauindustrie, wo ebenfalls Spiegel, Leisten oder Blenden dauerhaft mit dem Untergrund zu verankern sind.The invention is used not only in the automotive industry but also in Furniture and construction industry, where mirrors, strips or panels are also permanently with the Are to be anchored to the ground.
Wegen der hervorragenden Produkteigenschaften ist der Einsatz der Erfindung aber nicht auf die genannten Beispiele beschränkt. Vielmehr ist die Verwendung des Klebebandes in vielen Industriebereichen als Montagematerial möglich, wenn es gilt, auf einer relativ unebenen Oberfläche eine sichere Verbindung zwischen zwei Teilen unterschiedlichster Materialien zu schaffen.Because of the excellent product properties, however, the use of the invention not limited to the examples mentioned. Rather, the use of the adhesive tape possible in many industrial areas as assembly material, if necessary, on one relatively uneven surface, a secure connection between two parts of the most varied Creating materials.
Im folgenden soll die Erfindung anhand von Ausführungsbeispielen näher erläutert werden, ohne damit die Erfindung unnötig einschränken zu wollen.In the following, the invention will be explained in more detail using exemplary embodiments, without wanting to limit the invention unnecessarily.
In der Tabelle 1 sind die zur Herstellung des Trägers verwendeten Materialien aufgeführt,
und zwar jeweils mit Handelsnamen und Hersteller. Die genannten Chemikalien
sind alle frei im Handel erhältlich.
Die Ausgangsstoffe werden jeweils je nach Anwendungszweck des Selbstklebebandes
in unterschiedlichen Mischungsverhältnissen eingesetzt.
The raw materials are used in different mixing ratios depending on the application of the self-adhesive tape.
Im folgenden werden 11 Rezepturen für die Herstellung von erfindungsgemäßen Trägern jeweils in Form einer Tabelle dargestellt. Die Aufbereitung der verwendeten Materialien erfolgt dabei stets auf dem nachstehend beschriebenen Weg.The following are 11 recipes for the production of carriers according to the invention each represented in the form of a table. The preparation of the materials used is always done in the way described below.
Die Komponenten in den genannten Beispielen werden mit Ausnahme des Isocyanats, welches erst unmittelbar vor der Beschichtung mit Hilfe handelsüblicher 2-Komponenten-Mischtechnik zugegeben wird, in einem handelsüblichen Planetenmischer oder Dissolver zwei Stunden miteinander gemischt. Um ein blasenfreies Produkt zu erhalten, wird die Mischung während der letzten 10 min des Mischvorganges durch Anlegen eines Unterdruckes von kleiner 15 Torr entgast. Man erhält jeweils eine bei Raumtemperatur weiterverarbeitbare, strukturviskose Paste im Viskositätsbereich von 1 Pa*s bis 300 Pa*s.The components in the examples mentioned, with the exception of the isocyanate, which is only immediately before coating with the help of commercially available 2-component mixing technology is added, in a commercially available planetary mixer or dissolver mixed for two hours. To get a bubble free product the mixture is created during the last 10 minutes of the mixing process by applying a Vacuum of less than 15 torr degassed. One is obtained at room temperature Processable, pseudoplastic paste in the viscosity range from 1 Pa * s to 300 Pa * s.
Die Pasten werden nach Zudosierung des Isocyanats auf einer handelsüblichen Beschichtungsanlage auf handelsüblichem, beidseitig silikonisiertem Papier zu einer Bahn von 1 mm Dicke ausgestrichen und im anschließenden Trockenkanaldurchgang bei einer Temperatur von Raumtemperatur bis 120 °C und einer Verweildauer von 10 min bis 30 min zu einem Elastomer vernetzt. Die Träger haben nach der Härtung und einer anschließenden Lagerung von einer Woche bei Raumtemperatur eine Shore-A-Härte von 10 bis 60, eine Glasübergangstemperatur im Bereich von -60 °C bis -30 °C und eine Zugfestigkeit von größer 1 N/mm2 bei einer Reißdehnung von kleiner 500 %.After the isocyanate has been metered in, the pastes are spread onto a commercially available coating system on commercially available paper that has been siliconized on both sides to form a web of 1 mm thickness and then pass through a drying channel at a temperature of from room temperature to 120 ° C. and a residence time of 10 minutes to 30 minutes to form an elastomer networked. After curing and subsequent storage for one week at room temperature, the carriers have a Shore A hardness of 10 to 60, a glass transition temperature in the range from -60 ° C to -30 ° C and a tensile strength of greater than 1 N / mm 2 with an elongation at break of less than 500%.
Anschließend wird das Material in zwei Schritten beidseitig mit je 50 g/m2 der Polyacrylatmasse Durotac 280-1753 der Fa. National Starch beschichtet. Die Beschichtung mit der Lösungsmittelmasse erfolgt nach einer in-line Coronabehandlung direkt auf den Träger. Es wird bei 100 °C getrocknet und vernetzt. Das so erhaltene doppelseitige Klebeband wird einseitig mit Trennpapier abgedeckt.The material is then coated on both sides with 50 g / m 2 of the Durotac 280-1753 polyacrylate composition from National Starch on both sides. The coating with the solvent mass takes place after an in-line corona treatment directly on the carrier. It is dried and crosslinked at 100 ° C. The double-sided adhesive tape thus obtained is covered on one side with release paper.
In einem besonders bevorzugten Herstellverfahren wird die Polyacrylatmasse zuerst auf Trennpapier oder Trennfolie ausgestrichen und bei 100 °C getrocknet und vernetzt. Die Beschichtung mit der Polyurethanmischung erfolgt direkt auf die ausgestrichene Polyacrylatmasse. Noch vor der Härtung bzw. Vernetzung der Polyurethanmasse wird eine zweite Polyacrylatmasse, die sich ebenfalls bereits ausgestrichen, getrocknet und vernetzt auf Trennpapier oder Trennfolie befindet, gegen die Polyurethanmasse kaschiert. Anschließend erfolgt die Härtung bzw. Vernetzung der Polyurethanmasse im Trockenkanaldurchlauf bei einer Temperatur zwischen Raumtemperatur und 120°C, abhängig von der gewählten Polyurethanrezeptur und der Katalysatormenge. In a particularly preferred production process, the polyacrylate composition is first opened Release paper or release film spread and dried and crosslinked at 100 ° C. The Coating with the polyurethane mixture takes place directly on the spread polyacrylate mass. Even before the polyurethane composition cures or crosslinks second polyacrylate mass, which has also already been spread out, dried and crosslinked on release paper or release film, laminated against the polyurethane mass. The polyurethane mass is then cured or crosslinked in a dry channel run at a temperature between room temperature and 120 ° C of the selected polyurethane formulation and the amount of catalyst.
Das doppelseitige Klebeband zeichnet sich durch hohe Klebkräfte bei gleichzeitiger hoher Scherfestigkeit aus und die damit erzeugten Verklebungen besitzen eine exzellente Kälteschlagfestigkeit. Das Material dichtet gut gegenüber Feuchtigkeit ab.The double-sided adhesive tape is characterized by high adhesive strength with simultaneous high shear strength and the bonds created with it have excellent Low-temperature impact strength. The material seals well against moisture.
Claims (11)
- Pressure-sensitive double-sided self-adhesive tape comprising a backing which is coated on both sides with pressure-sensitive adhesive compositions and which is composeda) to a proportion of up to 50% by weight, in particular from 30 to 40% by weight, of a crosslinked, unfoamed polyurethanei) formed from hydroxyl-functionalized polybutadiene, polyesterdiol, polyester-triol, polyesterpolyol, polyetherdiol, polyethertriol or polyetherpolyol, polyetherdiamine, polyethertriamine, polyetherpolyamine and monohydric alcohol (monool), monofunctional amine (monoamine), polyethermonool, polyethermonoamine or from products derived from the four last-mentioned groupsii) and from diisocyanate or chemically derived isocyanate,iii) the polyurethane being free from plasticizer,b) to a proportion of from 50 to 70% by weight of fillers,c) and, if desired, further auxiliaries.
- Pressure-sensitive double-sided self-adhesive tape according to Claim 1, characterized in that an NCO/OH ratio of from 1.0 to 1.3, in particular from 1.0 to 1.1, is established in order to form the polyurethane.
- Pressure-sensitive double-sided self-adhesive tape according to Claim 1 or 2, characterized in that in order to form the polyurethane the proportion of OH and/or amine originating from the monool, monoamine, polyethermonool or polyethermonoamine as a proportion of the total OH is between 5 and 40%, in particular between 10 and 30%.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 3, characterized in that the hydroxyl-functionalized polybutadienes, the poly-esterdiols, the polyestertriols, the polyesterpolyols, the polyetherdiols, the polyethertriols, the polyetherpolyols, the polyetherdiamines, the polyethertriamines or the polyetherpolyamines have a molecular weight Mw ≥ 1000 g/mol.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 4, characterized in that carbon black, chalk, barium sulphate, talc, mica, pyrogenic silica, silicates, zinc oxide, solid glass microbeads, hollow glass microbeads and/or polymer microbeads are employed as reinforcing or non-reinforcing fillers.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 5, characterized in that auxiliaries employed arediscolouring or non-discolouring anti-ageing agents in the range from 0 to 5% by weight,light stabilizers in the range from 0 to 5% by weight,ozone protectants in the range from 0 to 5% by weight,siccatives, especially calcium oxide or molecular sieve zeolites, in the range from 0 to 10% by weight.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 6, characterized in that the backing has a thickness of from 0.1 to 50 mm, preferably from 0.4 to 20 mm.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 7, characterized in that a layer of coating material from the group of the polyamide, epoxy, phenolic, urea-formaldehyde, melamine-formaldehyde and polyurethane resins is applied between backing and adhesive coating.
- Pressure-sensitive double-sided self-adhesive tape according to Claims 1 to 8, characterized in that the backing carries the adhesive composition with a basis weight of from 10 to 250 g/m2, preferably from 40 to 150 g/m2.
- Use of a pressure-sensitive double-sided adhesive tape according to at least one of the preceding claims for sealing, especially for closing gaps.
- Process for preparing a pressure-sensitive double-sided adhesive tape according to at least one of the preceding claims, wherea) the adhesive composition, which has been applied to a release paper or a release film, dried and crosslinked, is introduced,b) the as yet unhardened, pastelike or liquid polyurethane composition, which has been prepared by means of customary techniques, is applied to the adhesive composition with the aid of two-component mixing technology,c) the second adhesive composition, which has been applied to a release paper or a release film, dried and crosslinked, is laminated to the polyurethane composition, andd) the polyurethane composition is cured or crosslinked at a temperature between 20°C and 120°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19733014A DE19733014A1 (en) | 1997-07-31 | 1997-07-31 | Self-adhesive tape |
| DE19733014 | 1997-07-31 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0894841A2 EP0894841A2 (en) | 1999-02-03 |
| EP0894841A3 EP0894841A3 (en) | 1999-03-10 |
| EP0894841B1 true EP0894841B1 (en) | 2003-05-02 |
Family
ID=7837496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP98113152A Expired - Lifetime EP0894841B1 (en) | 1997-07-31 | 1998-07-15 | Adhesive tape |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6129983A (en) |
| EP (1) | EP0894841B1 (en) |
| JP (1) | JPH11228919A (en) |
| DE (2) | DE19733014A1 (en) |
| ES (1) | ES2196432T3 (en) |
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- 1998-07-15 DE DE59808130T patent/DE59808130D1/en not_active Expired - Lifetime
- 1998-07-15 EP EP98113152A patent/EP0894841B1/en not_active Expired - Lifetime
- 1998-07-15 ES ES98113152T patent/ES2196432T3/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| US6129983A (en) | 2000-10-10 |
| DE59808130D1 (en) | 2003-06-05 |
| DE19733014A1 (en) | 1999-02-04 |
| JPH11228919A (en) | 1999-08-24 |
| EP0894841A3 (en) | 1999-03-10 |
| EP0894841A2 (en) | 1999-02-03 |
| ES2196432T3 (en) | 2003-12-16 |
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